Highly radiation-sensitive telomerized polyamides



United States Patent 3,471,386 HIGHLY RADIATION-SENSITIVE TELOMERIZED POLYAMIDES Gaetano F. DAlelio, South Bend, Ind., assignor, by mesne assignments, to PPG Industries, Inc., a corporation of Pennsylvania No Drawing. Filed May 18, 1966, Ser. No. 550,969 Int. Cl. C08f 1/16 US. Cl. 204-15915 24 Claims ABSTRACT OF THE DISCLOSURE The preparation of highly radiation-sensitive telomerized diacrylyl polyamides where said polyamides are treated by subjecting same to high energy ionizing radiation so as to produce three-dimensional crosslinked, insoluble, infusible polymers at relatively low doses of ionizing radiation.

This invention in general deals with radiation-sensitive polymers. Particulary it concerns viscous, soluble, flowable, relatively low molecular weight polymers, known as oligomers, which, when subjected to ionizing radiation become insoluble and infusible. More specifically, it deals with telomerized polyamides which, on irradiation, convert to three-dimensional crosslinked, insoluble, infusible polymers at relatively low doses of ionizing radiation.

The telomerized polyamides used of this invention are diacrylyl compounds containing amide groups or diacrylyl linear polyamides which are derived by the condensation of a glycidyl acrylate with (1) a linear condensation polymer of a saturated aliphatic (including cycloaliphatic) polycarboxylic acid and saturated aliphatic diamines or aminoalcohols or (2) a linear condensation polymer of a saturated aliphatic aminocarboxylic acid which has been reacted with a saturated aliphatic or dicarboxylic acid to give acid groups at both ends of the resultant condensation product. These telomerized polyamides have as end groups the highly radiation-sensitive group:

RI! CHFJJ-COOCHzCHCHzO- The term polyamides is used generically in this ap plication to include amide-ester copolymers as well as polymers in which all the condensation groups are amide groups.

One group of the telomerized polyamides of this invention can be represented by the general formula I CHFOCOOCHBCHOHZOOCRCO[AR'AOCRCO]11 OCHzCHCHzOOC =03:

wherein A represents O- or -NH-- but at least one A group per molecule represents NH, and preferably at least 50% of the A groups represent NH-; n has a value of 1 to 14; R represents a connecting linkage between two adjacent carboxyl radicals selected from the class consisting of a single valence bond and a divalent saturated aliphatic hydrocarbon radicalhaving 1 to carbon atoms; R represents a divalent saturated aliphatic hydrocarbon radical (including cycloaliphatic) having 1 to 10 carbon atoms; -R" represents hydrogen or CH R"" represents hydrogen or an aliphatic hydrocarbon radical (saturated or unsaturated) having 1 to 18 carbon atoms; and X represents hydrogen or an acyl group having the formula R""CO. The radical -AOCRCOA can be defined as the dicarboxylic radical derived from a saturated aliphatic acid such as oxalic, malonic, succinic, glutaric, adipic, decanedioic acids, etc., by reaction with a diamine, or an alkanolamine, or a mixture of a glycol and a diamine, or a mixture of an alkanolamine and a diamine. These diamines, alkanolamines and glycols can be represented by the formulas NH R'NH NH R'OH and HOROH, respectively. While the NH- group is preferred as the connecting amide group, it is considered equivalent for most purposes of this invention to use -NR' with R as defined above.

These highly radiation-sensitive telomerized polyesters are prepared from appropriate acrylyl derivatives such as the glycidyl esters,

I CHz=CCO0CHzCHCHg by reaction with car-boxyl terminated saturated aliphatic polyamides. In these bases, the glycidyl acrylate which is a derivative of the trihydric glycerine yields linear esteramides containing one free unreacted hydroxyl group. Thus, a dicarboxyl terminated aliphatic polyamide can be reacted with glycidyl acrylate to produce linear hydroxyl substituted radiation-sensitive polyesters, thus then RI! CHFl-COOCHISJHCHQOOCRCO RI! [NHR'OOCROOLOGHgCHOHgOOCt5=CHg This class of oligomers can be represented by the above formula in which )1. equal 1 to 14. When an alkanolamine or a mixture of a diamine and a glycol, or a mixture of a diamine and an alkanolamine is used in place of the diamine in the above reaction, the product obtained is similar to that of (1a) except that some of the -NH radicals have been replaced by O radicals. Thus where A represents either O or NH, the formula can be written as Formula 111 above.

In place of the diamine or alkanolamine, the corresponding alkylene imines,

can, when available, also be used, wherein R' is H or an alkyl group containing 1 to 10 carbon atoms.

Telomerized polyamides with a greater number of repeating segments, and therefore of higher molecular weight than the simplest polyamides, are prepared by increasing the ratio of the n, moles of dicarboxylic acid and the m+l moles of diamine or aminalcohol to the 2 moles of acrylic acid to maintain the molar ratio of diacidzdiamine, etc., acrylic at n:(m+1):2. Thus it may be seen that the simplest polyamide is obtained with one mole of diacid; two moles of diamine, etc., and two moles of acrylic acid. When the value of n. for the dicarboxylic acid is increased to 2, the value for the diamine becomes 3 and that for the acrylic function remains constant at 2.

3 4 Another group of the telomerized polyamides of this ilarity in the structure of the polyamide of this invention invention can be represented by the general formula with the structure of the polyamide to which it is being added facilitates the blending and makes it more compatible therewith, resulting in less destruction of or de- CHFCCOOCHCHCHZOOCRCOUROCM 5 traction from the properties of the original polymer. This X permits the blending of a crosslinking agent of improved R" compatibility and permits subsequent crosslinking by OOH2OCHZOOC$ZCHZ (1b) radiation without any disruption of or detraction from the basic properties of the original polymer. Consequently X the improvements effected by crosslinking are not offset wherein X and n are defined above; in any manner by the presence of incompatible groups or is a divalent aliphatic hydrocarbon radical of 4 to 10 groups which are less stable or have properties different carbon atoms preferably having at least 4 carbon atoms f o those of the amide groups of the base polymer. in the linear chain between its two valencies; and there I i of th f t th t th di ti dosage previously are at least two -NH- groups in t oly mid p required to effect any degree of crosslinking with most sented by A. polymers was so high as to be accompanied by degrada- The Value 0f the number of repeating units Within tion of the polymer, particularly with nylon, it is particuthe bracket of the formula can be determined or controlled larly important that blending with the' telomerized polyby various methods. For example, if caprolac am is amides of this invention permits crosslinking of nylon and used as the starting material the number of moles of other aliphatic polymers to be effected at very low radiacaprolactam added per mole of Water used to Start the tion dosages, as described more fully hereinafter, and

reaction will determine the value of n. For example, if thereby avoid degradation of the polymer.

three moles or five moles of caprolactam are used per mole While the telomerized polyamides of this inv ti of water, the value of n in the formula i l be 3 r have a particular utility with polyamide resins such as respectively. If an amino acid is used, or an ester of the nylon and polycaprolactamide, they can be used with aminoacid, the vapors from the reaction can be convarious other types of polymers, such as polyesters, both densed in an ice trap or in a Dean-Stark trap and the resaturated and unsaturated, including maleic-ethylene glyaction continued until the theoretical amount of water or col, phthalic-ethylene glycol, polyvinyl acetate, methyl alcohol has been recovered to give the desired degree of methacrylate, polyvinyl chloride types, etc.

polymerization. Polyamide resins for which the telomerized polyamides Since the terminal groups in the aminoacid or caproor diacrylyl glyceryl polyamides of this invention are lactam polymerization product differ from each other, particularly useful in blending for radiation treatment it is necessary to add a dicarboxylic acid or preferably can be represented as consisting essentially of a plurality the anydride to convert the polymer to one having two of repeating units having one of the following formulas: terminal acid groups that can be reacted with the glycidyl a R CONH- acrylate, etc. and

It is also possible to convert or combine two smaller units into one having two acid terminal groups by re- R NHOCR CONH action withadicarboxylic dihalide. For example: wherein R groups are divalent saturated aliphatic hy- 2H[NHRoo]..oH 11(0001); Ho[ooRNH]nocRoo[NHRC0]n0H With the hydroxy radicals of the above formula converted drocarbon radicals of 4 to 10 carbon atoms and adto OX radicals and R, R", R", and X as defined above, vantageously have at least 4 carbon atoms in the linear this formula will represent the third group of diacryl telochain of the repeating unit. The formula -RCONH- merized polyamides of this invention. In this formula n' represents a polyamide repeating unit derived from an and n" each have a value of at least 1 and n'+n" is no aminocarboxylic acid such as NH (CH COOH or from greater than 14. caprolactam. The second of the above formulas represents A typical synthesis of the group 112 telomerized polypolyamide repeating units in polyamides derived from amides or amide-esters of this invention is illustrated by the reaction of aliphatic diamines with aliphatic dicarbthe following reaction: oxylic acids, such as hexamethylene diamine and adipic (n+1)R(COOH)z+ nR(NHz)2 HOlOCRCONHRNH1nOCRCOOH RI! 2CH2=( 3COOCHzCH'CHz O R RI! CH2=( 3COOCHgCHCHzO[OCRCONHRNHLOCRCOOCHzCHCHzOOCfJ=CHg The telomerized polyamides of this invention are particacid which are used in the prepartion of nylon 66 which ularly useful for blending with various types of polyis polyhexamethylene adipamide. These polyamides can amides, particularly those which are not crosslinked by have molecular weights of 500 or more for the purpose of radiation or which require such a high degree of radiation this invention although there is no practical purpose in for crosslinking as to be accompanied by decomposition, using polymers having molecular weights over 100,000. A degradation, or discoloration. Where the telomerized polypreferred molecular weight range is 10,000 to 50,000.

amide of this invention is blended with a polyamide sub- Depending on the nature of R, R and R" the viscosity stance such as a nylon or polycaprolactamide, the sim of these telomerized polyamides increases from about 5 6 to 9000 centistokes at 20 C. as the value of It increases of a diamine, R'(NH and then two moles of a glycidyl from 1 to 14. Also depending on the values of n, R and acrylate, R", the molecular weight of these telomerized polyamides will vary from about 275 for the lowest one at a value of n1=1 to about 8800 for nequal to 14 when the di- CHz=J-COOOH Cfi-CH acid is decanedicarboxylic acid and the diamine glycol or 5 aminoalcohol has 14 carbon atoms. to give a product of the general formula cape-coo CHzCHCHqOOCROONHR'NHOCRCO o CHnCHCHzOOC-C=CH:

n" x x a" The hydroxy-substituted oligomeric acrylyl terminated for example,

polyamides represented broadly by Equations la and 1b CHFCHCOOCHzCHCHZOOCCHZCHzCONH have specific and improved utility especially when polymerized in the presence of cellulose such as wood, paper, x

fibers, fiber board, etc., in the form of a coating, im- 15 H: pregnant or bonding agent. The presence of the alcoholic CH =CHCOOCHzCHCHzOOCCHzCHzCONH hydroxyl causes improved wetting of cellulose and because X of hydrogen bonding of the hydroxyl group with the cel-. I lulose, yields improved adhesion compared to the unsub- Instead of the f Q 2 u1table dew/a stituted oligomeric polyamides represented by Formulas 0 W such as y ae d chlondes, or omega 1a, and ammoalkyl amides may be used in the synthesis of these In those cases where the presence of these hydroxyl polyamides, also insteaji P the diamines 2)a groups is not desired or is detrimental to such properties the correspondmg alkylene lmmes: as dielectric constant or power factor, the hydroxyl m m groups can he converted to ester groups by acylation with aliphatic acids, R""COOH wherein R"" is H or an aliphatic saturated or unsaturated hydrocarbon group con can, when available, also be used, wherein R is H or an taining 1 to 18 carbon atoms, such as formic, acetic, propalkyl group containing 1 to 10 carbon atoms.

ionic, butyric, acrylic, methacrylic, oleic, stearic acid, etc., Telomerized polyamides with a greater number of reor their anhydrides forming a class of oligomeric polypeating segments, and therefore of higher molecular amides suitable in the practice of this invention, thus: weight than the simplest polyamides, are prepared by in- I CHFC 00 o omoHcIno 0 o-n-o OIAR'AO 0R0 0],,o cHzt lncmo 0 c 5:011, 2RC 0 0H H OH RI! RI! oHFo 0 0 o omoncmo o C-R-C 0[AR'AO CRO 0],,0 CHzCHOHzO 0 0i1=ona (2a) 0 c RI!!! 0 C RI!!! I The acetyl derivative forms of the telomerized polycreasing the ratio of the n moles of diol and the 11+ 1 amides of Formulas 1b and 1c are similarly prepared from moles of dicarboxylic acid to the 2 moles of glycidyl the corresponding hydroxy compositions. acrylate to maintain the molar ratio of diaminezdiacid:

Acrylation of the hydroxyl substituted telomerized polyglycidyl acrylate at n: (n+1) :2. Thus it may be seen that amides of Equation la by means of an acrylic acid, or its a simple polyamide is obtained with one mole of diamine, acrylyl anhydric or chloride produces a class of teloetc.; two moles of diacid and two moles of glycidyl acrymerized radiation-sensitive polymers which, because of the late. When the value of n is increased for the diamine, increased number of acrylyl groups, shows an even more etc., to 2, the value for the diacid becomes 3 and that for improved response to ionizing radiation, thus the acrylic function remains constant at 2.

RI! RI! RI! l OHFAIOOOCHzCHCHzOOC-R-COMRAOCRCOLO CH CHCH O0CC=CHz (CHFC-COhO H H RI! R I I CH2=CCO0CHzGHCHzO0C-R-C0[ARAOCRCOhOCHgOHCH 00OC=CHa (3a) R RI! 5 l 0H2: -C 0-0 0-0 CC=CH2 Simple telomerized polyamides of this invention can be The linear polyamides can be prepared by various types prepared from the reaction of two moles of a saturated of standard reactions used in preparing amides starting aliphatic dicarboxylic acid, R(COOH) with one mole with acids or their anhydrides or acid halides and di- 3,471,386 l 7 v t p l s amines, etc. The conditions used are those appropriate increased froml to 14. Also depending on the values of for the normal reaction of amines with acids, anhydrides n, ,R' and R", the molecular weight of these telomerized and acid halides to form amides, and also those normally esters will vary from about 275 for the lowest one at a used for the reaction of the glycidyl group with acids. value of 11:1 to about 8800 for n equal to 14.

2R(COOH)1 R'(NH2)2 HOOCRCONHRNHOCRCOOH I v CHFCCOOCHzCHCH; R" l R" R" o -CHz=('JC 0 C-HzOHCHzO o CRCONHRNHO CRCO 0 CHtcH0H2o00JJ=0He This product can be converted to compounds in which X Typical examples of the various NH;-R'NH direpresents an acyl radical by reaction with anappropriate amines that can be used in synthesizing the telomerized acyl halide such as acrylyl chloride, or acyl anhydride such polyamides of this invention areethylene diamine, trias acetic anhydride, to give the desired acyl derivative. methylene diamine, tetramethylene diamine, 2,3-diamino- CHz=C CO 0 CHZCHCH:

CHFCCO O CHZCHCHzO O CRCONHR'NHO CRCOO CHzQHCHzOO C C=CH2 R" H H CH2CHCH:O O CRCONHRNHO CRCO O CHz-CH-CH:

H H H H BBSBlZCHFCCOCl RI! I CH =CCOOCHgCHCHzOOCRCONHRNHOCRCOOCH2CHCHzOOCC=CH: R H ()H R In the above formulas the derivative portion of the butane, 1,4-diaminobutane,1,4-diamino-2-ethylbutane, 1,6- glycidyl acrylate component are represented by the strucdiaminohexane, 1,8 diaminooctane, 2,10 diaminodecane, 1,4 diaminocyclohexane, 1,4 bis(aminomethyl) cyclohexane, 1,3 diamino'cycloheptane, 2,2 diethyl- 1 X propanediamine 1,3, 2,2 dimethyl-propanediamine-1,3,

3 methylpentadiamine 1,4, 2,2 diethylbutanediamine- H 1t 18 recogmzed that h oxlrjme g of the y- 1,3, 4,5 diaminononane, pentamethylene diamine, heptacldyl group y react 50 that 150mm1c Structure methylene diamine, nonamethylene diamine, decamethyl- GH-.=OCOOCH;CH ene diamine, diethylene triamine, triethylene tetramine,

CIJHBOX propylene diamine, dipropylene diamine, 2-ethylhexanediamine 1,3, etc. Alkylene imines can also be used to give may be formed. It is intended that both of these isomeric correspondmg glycol denvauves Such as Propylene mime structures are covered by the various formulas given hereethylene irflinea imine While P inabove such as dlethylene triamrne, etc. have an intermedlate 0ligomers in which the value of n is larger than 1 are aminf) group befween the termin al 31mins groups they are readily repargd by the ame reactions as given herein- COnSldCI'Cd equlvalent t0 the dlamrnes listed above for above by simply changing the ratio of the diamine, etc., the P p of this inventionto the desired value of n and that of the diacid to n+1 yp examples f various alkanol mines that can be while maintaining the molar quantity of the acrylic moiety used in synthesizing the telomerized polyamides of this at 2, thus invention are: ethanolamines, propanolamines, butanol- (n+1)R(COOH)2 nR'(NH=)'z HOOCRCONHRNHOCRCOBOH fill 2CHZ=CCOOCHICHCH2 R RI! CHFJJCOOomoHcmooonoolNHa'Nfio012001,,0 CHzCHCH OOOiJ=CH R! RI! CH:=( 1COOCHiCHCHgOOGRCO[NHRNHOCRCO]uOCHzCHCHgOOCiJ=CHs RI! IICO RI! [I00 Corresponding reactions can be performed to produce amines, hexanolamines, decanolamines, etc., such as 2- the 1b and 10 types of telomerlzed polyamrdes. aminoethanol, Z-aminopropanol-l, 3- aminopropanol-1, '3-

Depending on the nature of the R, R and R" the VlS- aminopropanol-Z, 4-aminobutanol-l, S-aminobutanol-Z, 4- cosity of these telomerized polyamides increases from aminopentanol-l, 6-arninohexanol-1, 7-aminooctan0l-2, 9-

about 100 to 9000 centistokes at 20 C. as the value of n aminodecanol-Z, IO-aminodecanol-l, etc.

Typical glycols that can be used in making mixed amide-ester polymers include: ethylene glycol, trimethyl ene glycol, tetramethylene glycol, 2,3-dihydroxy-butane, hexamethylene glycol, decamethylene glycol, 2,2-diethylprpanediol-1,3, diethylene glycol, triethylene glycol, dipropylene glycol, 2-ethylhexanediol-1,3, etc.

Typical examples of the various HOOCR-COOH acids that can be used in preparing the telornerized polyamides of this invention are oxalic, malonic, succinic, adipic, glutaric, sebacic, 2-methyl succinic, pimelic, 2,3- dimethyl succinic, suberic, hexyl succinic, 1,2-hexahydrophthalic, 1,3,- hexahydrophthalic, 1,4-hexahydrophthalic, azelaic, 1,1-cyclobutanedicarboxylic, trans-1,4-cyclohexanedicarboxylic, 3,3-diethyl glutaric, 3,3-din1ethyl glutaric, 2,2-dimethyl succinic, 2-ketoglutaric, diglycollic acids, etc. i

Aminoacids suitable for use in making the telomerized polyaniides include the following saturated aliphatic aminoacids: S-arninopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, S-aminocaprylic acid, 10 aminodecanoic acid, etc.

It is most important to note that the various classes of telornerized polyamides used in the practice'of this invention contain only saturated aliphatic hydrocarbon structures in the .segments derived from the polycarboxylic acids and the diamines, glycols and aminoalcohols. It is because of this aliphatic character that these telomerized polyamides" are highly. responsive to ionizing radiation, and in fact, replacement of any of the aliphatic polycarboxylic acids by aromatic carboxylic acids are replacement of the aliphatic diamines, etc. by aromatic amines, etc., decreases the response toionizingirradiationto such a point that they are not economically feasible. i

As an example, the di'rnethacrylyl glyce'ryl telomerized polyethylene succinamides,

at least equivalent to about 100,000 electron volts. While various types of irradiation are suitable for this purpose, such as X-ray and gamma and beta rays, the radiation produced by accelerated high energy electrons has been found to be very conveniently and economically applicable and to give very satisfactory results. However, regardless of the type of irradiation and the type of equipment used for its generation or application, the use thereof in the practice of the invention as described herein is contemplated as falling within the scope of this invention so long as the ionization radiation is equivalent to about 100,000 electron volts.

While there is no upper limit to the electron energy that can be so applied advantageously, the eiiects desired in the practice of this invention can be accomplished without having to go above about 20,000,000 electron volts. Generally, the higher the electron energy used, the greater is the depth of penetration into the massive structure of the materials to be treated, and the shorter is the time of exposure required to accomplish the desired result. For other types of irradiation, such as gamma and X-rays, energy systems equivalent to the above range of electron volts are desirable.

It is intended that the term irradiation include what has been referred to in the prior art as ionizing radiation which has been defined as radiation possessing an energy at least sufficient to produce ions or to break chemical bonds and thus includes also radiations such as ionizing particle radiation as well as radiations of the type termed ionizing electromagnetic radiation.

The term ionizing particle radiation has been used to designate the emission of electrons or highly accelerated nuclear particles such as protons, neutrons, alpha-particles, deuterons, beta-particles, or their analogs, directed in such a way that the particle is projected into the mass to be CH CCO O CHzCHCHzOIO C (CH2)CONHCHzCHzNH]aOC (CHz)zCO O CHzCHCHzO O C O=CH CB2: OH,

H CH:

irradiated. Charged particles can be accelerated by the aid of voltage gradients by such devices as accelerators v I g v I CH OCOOCHzCHCHgOIOCCsHiCONHCHzCHzNHhOCCdEhCOOCH OHCHzOOCC=GHz and the corresponding xylyl derivative both require 12 and 14 megarads respectively, to become insoluble and infusible.

This difference is surprising particularly because'these three telomerized polyamides all cure with radical initiators such as with 1% benzoyl peroxide in about 90 to 95 seconds at 100 C., and with redox systems of cobalt acetate and tertiary butyl hydroperoxide in three to three and one-half hours at room temperature. The difference is due apparently to the fact that aromatic ring compounds such as phenyl, naphthyl and the like are energy sinks for irradiation. v s

It will be noted too that the aliphatic hydrocarbon struc tures in the polycarboxylic and polyamide segments are saturated. This is for the purpose of avoiding'brittleness and reducing susceptibility to oxidation and discoloration in the irradiated products. By having the unsaturation only at the ends of the telomerized diacryl polyamide more ductile products are obtained upon irradiation and resultant crosslinking, particularly where there are long saturated chains between the connecting acrylyl groups.- Also by having only the acrylyl unsaturation in these compounds there is less residual unsaturation after irradiation and therefore less susceptibilityto oxidation and discoloration. 7

The term irradiation, as used herein, means high energy radiation and/or the secondary energies resulting from the conversion of this electron or other particle energy to neutron or gamma radiation, said energies being with resonance chambers, Van de Graatf generators, betatrons, synchrotrons, cyclotrons, etc. Neutron radiation can be produced by bombarding a selected light metal such as beryllium with positive particles of high energy. Particle radiations can also be obtained by the use of an atomic pile, radioactive isotopes or other natural or synthetic radioactive materials.

Ionizing electromagnetic irradiation" is produced when a metallic target, such as tungsten, is bombarded with electrons of suitable energy. This energy is conferred to the electrons by potential accelerators of over 0.1 million electron volts (mev.). In addition to radiations of this type, commonly called X-ray, an ionizing electromagnetic radiation suitable for the practice of this invention can be obtained by means of a nuclear reactor (pile) or by the use of natural or synthetic radioactive material, for example, cobalt 60.

Various types of high power electron linear accelerators are commercially available, for example, the Arco type travelling wave accelerator, model Mark I, operat-v ing at 3 to 10 million electron volts, such as supplied by High Voltage Engineering Corporation, Burlington, Mass, or other types of accelerators as described in United States Patent No. 2,763,609 and in British Patent No. 762,953 are satisfactory for the practice of this invention.

In the following examples, the radiation doses are reported in megarads, which represent 1,000,000 rads. A

1 1 rad is defined as the unit of absorbed dose and is equal to 100 ergs per gram.

Many monomers as well as polymers have been subjected to ionizing radiation to convert them to improved or modified products. However, irradiation processes have been primarily of scientific interest, and very little use of such irradiation polymer processes has been made industrially. This is primarily due to economic factors because of the cost of the ionizing radiation delivered to the system to be treated. For example, the well-known low-cost polyester systems which consist of a mixture of about equal parts by weight of styrene monomer and unsaturated alkyd resin prepared from maleic or fumaric anhydride, phthalic anhydride and ethylene glycol or diethylene glycol can be more economically polymerized by free radical initiators than by ionizing radiation which requires about 25 to 40 megarads, depending on the formulation.

Such systems can be improved somewhat, however, by elimination of phthalic anhydride in the formulation of the polyester and substituting the more expensive monomeric acrylic compounds for the styrene. Even in such systems, the economic factors are unfavorable not only because of the much higher cost of the mixture but because of the high volatility of the acrylic or methacrylic monomeric compounds used. Even in such cases the irradiation dose required is of the order of 18 to 29 megarads and the systems are highly inhibited by oxygen. The addition of substances such as acetone or methyl ethyl ketone can reduce the required dose to 12 to 14 megarads. Even then the products possess the undesirable odor of unpolymerized acrylic monomer.

In contrast, by the use of the acrylyl glyceryl telomerized polyamides of this invention, crosslinked, insoluble, infusible polymers can be prepared readily by subjecting the polyamides to ionizing radiation in doses of less than megarads and in some cases to doses of 0.5 megarad or less, generally preferably at least about 1 megarad. Irradiation dosages in this range are economical.

Furthermore, the acrylyl components in these telomerized polyamides are located at the ends of the polyamide chains where they can more effectively crosslink. More important, the acrylyl components comprise a minor portion of the composition, and are particularly economical when the value of n in these telomerized polyamides is at least 2. In addition, because the molecular weight of the telomerized polyamide is much higher than a corresponding simple monomer such as methyl methacrylamide or ethyl acrylamide, it can function in a single molecule both as monomer and as polymer.

Even more surprising is the fact that this property of crosslinking at economical radiation doses is maintained when these telomerized polyamides are admixed with polyamide resins such as nylon, polycaprolactam, polyacrylamide, etc., alone or in the presence of other polymers provided the polyamide resin and the other polymers are of the nonaromatic type, that is, they are free of aromatic rings which act as energy sinks and retard the crosslinking reaction. One of the advantages of these diacrylyl glyceryl polyamides is their compatibility with various types of resins, particularly polyamide types.

A few illustrative examples of suitable polymers which may be dissolved in or mixed with the telomerized polyamides of this invention along with the polyamide resins and other types of resins are the nonaromatic type polymers such as polyvinyl acetamide, polyacrylamide, polymethylacrylamide, polyhexamethylene adipamide, polyethylene adipamide, polyethylene azelamide, polyethylenediacrylamide, polyvinyl acetate, polyethyl acrylate, polymethyl methacrylate, cellulose acetate, cellulose butyrate, ethyl cellulose, polyethylene adipate, polyethyene azeleate, polydecamethylene succinate, polydecamethylene sebacate, etc. The telomerized polyamides are also compatible with polyvinyl chloride, particularly upon the application of moderate heat.

The telomerized polyamides of this invention are particularly useful as coating compositions on all types of substrates, including cellulose in its various forms, such as paper, wood, paper board, wood board, wood pulp, regenerated cellulose in film or fiber form, laminates of various types including those prepared from fibrous fillers bonded with urea, melamine, epoxy and polyamide resins, plaster board, concrete in its various forms such as slabs, blocks and the like. They may also be used as impregnants for porous bodies such as the compositions hereinabove named,'as well as for synthetic and natural sponges, etc. Particularly do they find use as bonding agents and adhesives for solid, porous and foamed bodies. They can be used alone or admixed with each other or with other copolymerizable monomers, unsaturated or saturated polymers, in the absence or presence of dyes, pigments, plasticizers. For coating, impregnating or adhesive compositions where the presence of small amounts of solvent in the cured composition is not objectionable they can be mixed with volatile or nonvolatile solvents of a nonaromatic nature best suited to the particular application. The products resulting from the irradiation of the telomerized polyamides of this invention can vary from soft flexible bodies to hard rigid masses.

The telomerized radiation-sensitive polyamides of this invention are particularly useful in the preparation of copolymers with polyamide alkyd resins, such as nylons of the various types, polycaprolamide, polyacrylamide. In carrying this portion of the invention into effect, an amidification product of a diamine and a dicarboxylic acid is first prepared in accordance with techniques now well known to those skilled in the polyamide art.

Any aliphatic diamine alcohol containing at least two amidifiable aliphatic amine groups, or mixtures of such amines, can be used in preparing the polyamide resins. Examples of appropriate diamines are ethylene diamine, di-, tri-, and tetraethylenediamine, 1,4-diaminobutene-2, bis(aminomethyl)cyclohexane, diaminocyclohex'ane, etc. Any nonaromatic polycarboxylic acid, or mixtures of such acids, can be reacted with the diamine, etc. to form the polyamide resin. Examples of such polycarboxylic acids are succinic, adipic, glutaric, pimelic, sebacic, *azelaic, suberic, tricarballylic, etc. Anhydrides of these acids, if available, can also be used. The term polycarboxylic acid as used generally herein is intended to include the anhydrides of the acids.

Aminoacids that can also be used in making polyamides suitable for the practice of this invention include the following saturated aliphatic aminoacids: S-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, S-aminooctanoic acid, IO-aminodecanoic acid, etc.

The telomerized radiation-sensitive polyamides of this invention are also useful in the preparation of copolymers with unsaturated alkyd resins. In carrying this portion of the invention into effect, an esterification product of a polyhydric alcohol and an alpha,beta-unsaturated polycarboxylic acid is first prepared in accordance with techniques now well known to those skilled in the alkyd resin art.

Any aliphatic polyhydric alcohol containing at least two esterifiable aliphatic hydroxy groups, or mixtures of such alcohols, can be used in preparing the unsaturated alkyd resins. Examples of such polyhydric alcohols are ethylene glycol, di-, tri-, and tetraethylene glycols, thiodiglycol, glycerine, pentaerythritol, 1,4-dihydroxybutene- 2, dimethylol cyclohexane, dihydroxycyclohexane, etc. Any nonaromatic alpha-unsaturated, alpha,beta-polycarboxylic acid, or mixtures of such acids, can be reacted with the polyhydric alcohol or alcohols to form the unsaturated alkyd resin. Examples of such polycarboxylic acids are maleic, fumaric, citraconic, mesaconic, acetylene dicarboxylic, aconitic, cyclohexane dicarboxylic, etc., itaconic and its homologues, as, for instance, alpha methyl itaconic acid, alpha,alpha-dimethyl itaconic acid, etc. An-

13 hydrides of these polycarboxylic acids can also be employed.

In some cases, instead of using an unmodified, unsaturated alkyd resin, an unsaturated alkyd resin can be used which has been internally modified by replacing a part, say up to about 75 mole percent, of the unsaturated polycarboxylic acid with saturated aliphatic polycarboxylic acids, such as succinic, adipic, glutaric, pimelic, sebacic, azelaic, suberic, tricarballylic, etc.

The esterification products of polyhydric alcohols with ethylenic polycarboxylic acids, or with aliphatic polycarboxylic acids, can be further modified by introducing as a reactant in the preparation of the alkyd resin, a monoesterifiable compound or compounds, more particularly a saturated or unsaturated normal or isomeric monohydric alcohol, or mixture thereof, a saturated or unsaturated monocarboxylic acid, or mixture thereof, or both such esterifiable monohydroxy organic compounds as well as by the use of hydroacids.

Examples of non-aromatic monohydric alcohols which can be used as modifiers of the alkyd resin are propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, octyl, decyl, dodecyl, tetradecyl, cetyl, octadecyl, cyclo'hexyl, cyclopentyl, etc. The use of methyl and ethyl alcohol is not precluded, but in general these alcohols are less satisfactory because of their lower boiling points. As monobasic acids there can be used, for example, the unsubstituted saturated and unsaturated normal or isomeric monocarboxylic acids containing only one esterifiable group, such as acetic, propionic, butyric to stearic, inclusive, hexahydrobenzoic, hexahydrotoluic, acrylic, methacrylic, furoic acids, etc.

The monoesterifiable compounds can be introduced into the esterification before, during, or after the esterification of the polyhydric alcohol with the polycarboxylic acid under conditions that promote interesterification of the monoesterifiable compound with the incompletely esterified polyhydric alcohol-polycarboxylic acid product. That is, the monoesterifiable compound is introduced into the reaction mass before all of the acid groups of the polyhydric acid, or all of the alcohol groups of the polyhydric alcohol have been esterified.

The term unsaturated nonaromatic alkyd resins, as used generally herein and in the appended claims, is intended to include within its meaning both unmodified esterification products of a nonaromatic polyhydric alcohol with a nonaromatic alpha-unsaturated, alpha,betapolycarboxylic acid and esterification products of these components which have been modified, for example, as briefly described hereinabove. An alternate term is unsaturated aliphatic alkyd resins (including cycloalip'hatic types).

To achieve copolymerization of the unsaturated alkyd resin with the telomerized polyesters of this invention, a solution or mixture of the unsaturated alkyd resin in the telomerized polyesters is first elfected. Copolymerization of the components of the mixture is achieved rapidly and advantageously by ionizing radiation, such as by atomic radiation from a reactor, or from cobalt 60, or by means of high energy electrons generated by an electron linear accelerator.

Typical examples of unsaturated alkyd resins are:

Alkyd resin A-Ethylene glycol itaconate Parts (by wt.)

Ethylene glycol Itaconic acid 14 Alkyd resin B-Ethylene glycol maleate Parts (by wt.) Ethylene glycol 31 Maleic anhydride The compounds are mixed and heated as in the prepara: non of alkyd resin A to C., and held at that tempera ture for four to six hours.

Alkyd resin C-Acetic acid-modified diethylene glycol maleate Parts (by wt.) Diethylene glycol 106 Maleic anhydride 88 Acetic anhydride 10 The ingredients are mixed together and refluxed for one hour in an inert nitrogen atmosphere after which the reaction mixture is brought to C., which temperature is maintained for four to sixhours.

It will be understood, of course, that this invention is not limited to the use of the specific unsaturated alkyd resins mentioned above and that a broad modification of the nature of the copolymer is possible by using other unsaturated aliphatic alkyd resins or mixtures of such resins. As illustrative examples of other unsaturated alkyd resins, the following esterification products can be used, as illustrated in alkyd resins D to I. Aromatic alkyd resin J is included for comparison.

Alkyd resin components: Parts Diethylene glycol 160 Maleic anhydride 147 Diethylene glycol 106 Itaconic acid 130 Glycerine 18.4

Itaconic acid 39.0

Ethylene glycol 6.0

Maleic anhydride 19.6

Hydroxypropyl acrylate 26.0

Ethylene glycol 20 Maleic anhydride 29.4

Succinic acid 3.3

Diethylene glycol 30.6

Maleic anhydride 17.6

Itaconic acid 15.6

Diethylene glycol 30.3

Maleic anhydride 13.2

Phthalic anhydride 21.7

In many cases, instead of polymerizing a single telomerized polyamide with a single aliphatic polyamide resin or aliphatic unsaturated alkyd resin, mixtures can be used of two or more telomerized polyamides with a single polyamide resin or unsaturated aliphatic alkyd resin, or a single telomerized polyamide with two or more aliphatic resins, or a mixture of two or more telomerized polyamides with two or more aliphatic resins. In conjunction with the aliphatic resins, comonomers can be used which are copolymerizable with the telomerized polyamide or with the aliphatic resins, or with both, for example, one or more telomerized polyamides can be used with one or more aliphatic resins together with methy methacrylate. I

In addition to, or in lieu of the methyl methacrylate, other comonomers or mixture of comonomers can be used, for example, the vinyl esters, that is vinylacetate, and the vinyl esters of saturated and unsaturated, and aliphatic, monobasic and polybasic acids, and more specifically the vinyl esters of the following acids: propionic, isobutyric, valeric, caprylic, capric, oleic, stearic, acrylic, methacrylic, crotonic, oxalic, malonic, succinic, glutaric, adipic, suberic, azelaic, maleic, fumaric, itaconic, mesaconic, hexahydrobenzoic, citric, trimesic, etc., as well as the corresponding allkyl, methallyl, etc., esters of the aforementioned acids.

Other suitable comonomers are the acrylic and alkacrylic acids and their derivatives, such as their esters, amides and corresponding nitriles, for example, acrylic acid, methyl acrylate, butyl acrylate, allyl acrylate, ethylene glycol diacrylate, ethylene diacrylamide, propylene diacrylamide, acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, etc.; the itaconic acid monoesters and diesters, such as the methyl, ethyl, allyl, dimethallyl, the maleic and fumaric acid monoesters, diesters and their amide and nitrile compounds, such as, ethyl allyl maleate, maleyl diamide, fumaryl dinitrile, dimethallyl fumarate, etc.; the ,ethers, such as methallyl allyl ether, vinyl allyl ether, vinyl methallyl ether, allyl crotyl ether, vinyl crotyl ether; cyanuric acid derivatives such as dialyl cyanurate, triallyl cyanurate, trivinyl cyanurate, or in general, triazine compounds having at least one polymerizable or copolymerizable unsaturated group attached directly or indirectly to the triazine ring, as well as the partial, soluble or fusible polymers of the hereinabove listed monomers, etc.

The modified aliphatic polyamide resins of this invention can be used alone or with fillers, dyes, pigments, opacifiers, lubricants, plasticizers, natural and synthetic resins or other modifying bodies in, for example, casting, molding, laminating, coating applications, and as adhesives, impregnants, and protective coatings.

In coating, impregnating and similar applications, the mixed monomeric or partially copolymerized materials, without added solvent can be applied to the object to be treated and polymerized, with or without the application of heat and pressure, to form the final insoluble polymeric composition in situ. These new synthetic materials can be used as impregnants for many porous bodies, such as cork, pottery, felts, or fabricated bodies with interstices, such as the windings of electrical coils, netted fibers, interwoven fibrous cotton or glass materials, etc. They can also be used for the production of wire coatings and winding tapes, and for protectively coating impervious articles, such as metals, or for coating and impregnating articles such as paper, wood, cloth, glass fibers in felted, woven or other form, concrete, linoleum, synthetic boards, etc. These new synthetic materials can also be employed in making laminated fibrous sheet materials wherein superimposed layers of cloth, paper, glass fabrics or mats, etc., are firmly bonded together with these new compositions. Also, these new mixtures comprising at least one telomerized polyamide of this invention and at least one aliphatic polyamide resin, with or without modifying agents, can be cast under pressure while being irradated.

In preparing the interpolymerization products of the aliphatic polyamide resin and the telomerized polyamide, the aliphatic polyamide resin can constitute as much as 98 to 99 percent by weight of the whole. In other cases the telomerized polyamide alone, or admixed with aliphatic comonomers or modifiers, can constitute as much as 98 to 99 percent by weight of the whole.

In general, the proportions of the components used in a particular formulation will depend upon the particular properties desired in the interpolymer. For most applications, it is preferred to use 30 to 90 percent of the unsaturated aliphatic polyamide resin and from to 70 percent of the telomerized polyamide, since within these ranges interpolymers best adapted for most commercial applications can be produced.

Within these ranges the new interpolymers have a wide range of properties. For example, depending upon the particular telomerized polyamide or mixture of telomerized polyamides used with the particular aliphatic polyamide resin the particular proportions thereof, the conditions of polymerization, such as the temperature, pressure, presence or absence of additives, etc., the irradiation dose, and the extent of polymerization, they can vary from soft flexible bodies to hard rigid masses of varying resistance to solvents.

In the intermediate stages of copolymerization, some form fluid compositions of varying viscosities and may be so used. For coating or impregnating applications where the presence of a small amount of solvent in the cured composition is not objectionable, the mixed starting component can be diluted with volatile or nonvolatile solvents or diluents best suited for the particular service application, and then can be polymerized after the application of the solution to the particular article to be coated or impregnated, or impregnated and coated. By suitable selection of the starting material and the conditions of the interpolymerization, interpolymers can be obtained in an insoluble, infusible state practically resistant to the destructive effect of other chemical bodies, such as acid, bases, salts, solvents, swelling agents, and the like.

When it is desired to modify the properties of the polymers of the telomerized polyamides of this invention, this can be accomplished by copolymerizing a mixture comprising at least one telomerized polyamide with at least one copolymerizable unsaturated ethylenic, or acetylenic hydrocarbon radical, more particularly, a CH =C radical, such as vinyl, allyl, methallyl, vinylidene, etc., or with a copolymerizable compound containing a CH= CH- or a CH=C or a C=C grouping, for example, as in vinylidene fluoride, vinylidene cyanide, vinyl propionate, maleic anhydride, or its esters and amides, methyl maleic anhydride, tetrafluoroethylene, etc.

Additional examples of copolymerizable comonomers are monomeric or partially polymerized vinyl esters, such as the acetate, propionate, etc.; vinyl ketones, methvinyl ketones, olefinic nitriles, such as acrylonitrile, methacrylonitrile, fumaryl nitrile, beta-cyano-ethylacrylate, acrylic and methacrylic esters, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, glycol dimethacrylate, allyl methacrylate, etc.; itaconic esters, for example, dimethyl itaconate, diethyl itaconate, diallyl itaconate; olefinic amides, for example, acrylamide, itaconamide, the maleic monoand di-amides, and the corresponding imides, etc., the vinyl ethers, for example, vinyl butyl ether, vinyl isobutyl ether, vinyl cyclohexyl ether, the dienes, etc., for example, butadiene, isoprene, dimethyl butadiene, etc.

In preparing copolymers of the telomerized polyesters with other polymerizable comonomers such as methyl methacrylate, acrylonitrile, and the like, the telomerized polyesters can constitute as little as 0.1 percent by weight of the whole, whereas in other cases, the telomerized polyamides alone can constitute as much as 98 to 99 percent of the whole. As in the case of the copolymers with aliphatic polyamide and polyester resins, the proportion of the components in a particular formulation will depend upon the particular comonomers used and the particular properties desired in the copolymer. The polymers and copolymers can be prepared most readily by ionizing radiation.

Various methods of practicing the invention are illustrated by the following examples. These examples are intended merely to illustrate the invention and not in any sense to limit the manner in which the invention can be practiced. The parts and percentages recited therein and all through this specification, unless specifically provided otherwise, refer to parts by Weight and percentages by weight.

EXAMPLE I In a suitable apparatus equipped with a stirrer, reflux condenser, inert gas inlet, heating mantle, and thermostatic control for the reactor, are placed 12 parts of ethylene diamine and 40 parts of succinic acid anhydride.

The apparatus is first deoxygenated by sweeping dry de-' oxygenated nitrogen through the apparatus and thereafter allowing a slow stream of nitrogen to pass through during the reaction. The mixture is heated to about 100 C. for about one hour'to give a quantitative yield of HOOCCH2CH2CONHCH CHgNHOCCHgCHgCOOH Then 51.2 parts of glycidyl acrylate and 0.25v art of t-butyl catechol are added and the reaction continued for about two hours to give the telomerized oligomer:

(a) CHFCHCOO CHzCHCHzO O C CH2CH2CONHCH2 CHNHO 000260200 CHzOHCHzO O C CH=CH2 This is a light-colored, resinous product.

(b) When an equivalent amount of glycidyl methacrylate is substituted for the glycidyl acrylate the corresponding methacrylyl derivative is obtained.

(c) When an equivalent amount of glycidyl acetate is substituted for the glycidyl acrylate the corresponding acetyl derivative is obtained.

EXAMPLE II and there are obtained the corresponding products in which the center OOCCH CH CONHCH CH NHOCCH CH COO- portion of the molecule is replaced respectively by:

(a') OOCCONHCH CH NHOCCOO (b) OOCCI-I CONHCH CH NHOCCH COO (c') OOC (CH CONHCH CH NHOC (CH COO (d') OOC(CH CONHCH CH NHOC (CH COO- (e') OOC (CH CONHCH CH NHOC (CH COO-- (f) OOC (CH CONHCH CH NHOC(CH COO- (g') OOC (CH CONHCH CH NHOC (CH COO (h') 0 O C (IJHCONHCH2CH2NHO C 01100 0--- CH CH (i') OOC(CH CONHCH CH NHOC(CH COO- (j') OOC(CH CONHCH CH NHOC(CH COO- 1 8 EXAMPLE III The procedure of Example I is repeated six times using respectively instead of the 12 parts of ethylene diamine:

(a) 14.8 parts of trimethylenediamine; (b) 28.8 parts of hexamethylenediamine; (c) 34.4 parts of octamethylenediamine; (d) 400- parts of 2,9-diaminodecane; (e) 12.1 parts of ethanolamine;

(f) 17.8 parts of 4-aminobutanol-1;

and there are obtained respectively:

(a') OH =CHCO O CHZCHCH O O C CHzCO2CONH(CH2)3 H NHO C GHzCHzCO O CHaCHCHzOO GCH=CH1 (b) CH2=CHCO OCHzC CHzO O C CH2OH2CONH(CH2)6 NHO C CHzCH2CO O CH2CHCHzO O CCH=CH2 (0) CH =CHCO O CHzC OHzO O C CH2CH2CONH(CH) NH0 0 CHzCHzCO O CH2CHCHZOOOCH=CHI (d') CH =OHCOO OHzC CHzOO CCHzCHzCONHCHflJHzh CHNHO C CHzCHzCO O CHZCHCHQO O CCH=CH1 ()H; H

(e') CHz=CHCO O OHzCCHgO O CCH3CHzCONH(CHz)2 O O C OHzCHaCO O CHzCHCHzO O C CH=CH2 (i') CH2=CHCOO CHzC CHzOO C CHZCHZCONH CH2 4 O O C CHzCHzCO O CHaOHCHzO O C CH=OH Similar results are also obtained with equivalent amounts of 2,3-diaminobutane, decamethylenediamine, 2,2-diethylpropane diamine 1,3, diethylenetriamine, 1,4-diaminocyclohexane, 1,2 diaminocyclohexane, 1,4 bis(aminomethyl) cyclohexane, etc.

EXAMPLE IV To the reactor of Example I there is added 24 parts of ethylene diamine and 50 parts of succinic anhydride (or 59 parts of succinic acid), and the mixture reacted at 180 C. for six hours or until titration of a sample with 1 N sodium hydroxide shows that it is substantially HOOC(CH [CONHCH CH NHOC (CH COOH Then there is added 25.6 parts of glycidyl acrylate and 0.25 part of t-butyl catechol and the reaction continued for another two hours to give the oligomer:

CH CHCO O CHzCHOHzO O C (CH2)2CO[NHCHzOHzNHO C (OH2)2C 0140 CHzCHCHzO O OCH=CH2 EXAMPLE V The procedure of Example IV is used except that 60 parts of ethylene diamine and parts of succinic anhydride are used instead of 24 parts and 50 parts, respectively, and there is obtained In a similar way by using 72 parts of ethylene diamine and 130 parts of succinic anhydride, there is obtained A mixture of 516 parts of the product of Example I, 204 parts of acetic anhydride and 1 part of tributyl amine are refluxed in a nitrogen atmosphere for one hour. Then the acetic acid by-product is removed by distillation under a reduced pressure of mm. and there remains in the reaction flask 597 parts of the product (a) CHz=CHCO O CHzC CHzO O C CHzCHzC ONHCHZ 00 C CH;

CHzNHO CHzCHzC O O CHzCHCHzO O C CH=CH When the above. procedure is repeated with equivalent amounts of the products of Examples II-V the correspond ing diacetyl derivatives are obtained.

EXAMPLE VII The procedure of Example VI is repeated except that instead of acetic anhydride there is used 252 parts of acrylic anhydride containing 1% of tributyl amine, and there is obtained (a) CH2=CHCOO CHzC CHzO O CCHzCHzC ONHCH2 O O C CH=CH2 CHzO CHzOHzC O O CHzCHCHzO O C CH=CH2 When the above procedure is repeated with equivalent amounts of the products of Examples II-V the corresponding tetraacrylyl derivatives are obtained.

EXAMPLE VIII By repeating the procedure of Examples VI and VII a number of times using molar equivalents respectively of the appropriate anhydrides, namely, methacrylic, stearic, methoxyacetic, acetic, acrylic and butyric anhydrides, the corresponding ester products are obtained.

EXAMPLE IX To the reactor of Example I there are added, in a number of respective experiments, appropriate proportions of ethylene diamine and succinic anhydride and reacted at 180 C. for six hours to give a series of products having the general formula wherein n equals 1, 3, 5, 10, 12, 14 and 15. These are in turn each reacted with two molar proportions of glycidyl methacrylate to give seven products respectively of the general formula CH CHFJJ CO 0 CHzCHCHzO O C(CH2)2C ()[NHCHz r CHnNHO C(CHDzCOhCHzCHCHfi O C C=CH2 H Where n=1 for Sample a, n=3 for Sample b, n=5 for Sample a, n=10 for Sample d, n=l2 for Sample e, n: 14 for Sample f, n=15 for Sample g.

EXAMPLE X The procedure of Example IX is repeated a number of times using molar equivalents of glycidyl acrylate instead of glycidyl methacrylate, and there are obtained seven products of the general formula CH2=OHCHOOOCHzCHCHzOOC(CH2)2CO[NHCH2 CHzNHOC(CH2)2CO]11CH2CHCH2OOCCH=CII2 H where n=1 for Sample a, n=3 for Sample b, n=5 for Sample 0', n=l0 for Sample d, n=l2 for Sample e, n=14 for Sample f, 11:15 for Sample g.

EXAMPLE XI The seven products of Example IX, a to g, inclusive, are treated with acetic anhydride by the procedure of Example VI and there are obtained the acetyl derivatives of the general formula CH (a) CHz= C C O O CH2CHOH2O O C(CH2)zC O [NHCH O O C CH CH CHzNHO C(CH2)2C OhCHzCHCHzO O C O =CHz 0 0 CH and when acrylic anhydride is used as the acrylating agent according to Example VII, there are obtained the respective products (b) CHe=Cll C O O CHZCHCHZO O C(CH2)2C 0 [NHCHz CH 0 o o CH=CH2 CHzNHO C(CH2)2CO]nCHgCHCHgOOCII=CH OCCH=CH2 with the values of 11 corresponding in each case to those of Example IX, where n has the original numerical value of l to 15.

EXAMPLE XII When in Example IX other saturated aliphatic dicarboxylic acids, such as glutaric, dodecanedicarboxylic acid, hexahydrophthalic, etc., are used instead of succinic anhydride, the corresponding hydroxy-substituted diacrylyl terminated polyamides are obtained. These hydroxy-substituted polyamides are readily acylated by the procedures of VI, VII and VIII.

EXAMPLE XIII The procedure of Example IX is repeated a number of times using equivalent quantities of an aromatic dicarboxylic acid, phthalic anhydride, instead of the aliphatic dicarboxylic succinic anhydride, and there is obtained a seres of products of the general formula CH2=C CO 0 CHzCHCHzOlO C 0,1140 ONHCHZCII NHLI O C CoIItC O O CHzCHCHzO O C C=Cllz in which It=l in Sample a, 11:5 in Sample I), n=10 in Sample c, n: 12 in Sample d.

21 EXAMPLE XIV The procedure of Example IX is repeated using equivalent quantities of an aromatic diamine p-xylylidenediamine, NH CH C H CH NH instead of ethylenediamine, and there is obtained a series of products of the general formula CH3 O 22 woodchip board and the whole irradiated to 4 megarads. There is obtained a finished board having the appearance of a fine grain, high gloss, varnished wood which is resistant to water, alcohol, acetone and most of the common I CH=JJCO O CH2CHCH2O O C CHz COINHCHgCuILCHzNHO C CHzCCOhO OH2(IJHCH OO CO: CH:

in which n =1 in Sample a, 11:5 in Sample b, 11:10 in Sample c, n=l in Sample d.

EXAMPLEVXV EXAMPLE XVI The tetraacrylyl-substituted polyamides of Examples VII and VIII are irradiated in an open container. These crosslink at irradiation dosages within the range of 0.90 to 1.4 megarads, indicating the extra sensitivity introduced into the diacrylyl telomerized polyamide by the introduction of two additional acrylyl groups.

EXAMPLE XVII The seven telomerized polyamides of Example IX are subjected to irradiation. Those having values of n from 1 to 14 crosslink under dosages increasing from 2 megarads for nz=1 to 4.6: megarads for n=14. For n=15, crosslinking occurs at '6.7.mega'rads, indicatingan economical upper limit for values of rt being less than 15. When, however, an average value of less than 15' can be obtained by mixtures of polyamides of n being smaller than 15, for example 11:1 to' 12 with afpolyamide of n='15, for example equal mixtures of amides'of 'n=l5 with amides of n'=1 and 5, respectively, crosslinking occurs at 3.1 and 4.2 megarads, respectively. I

Irradiation of the telomerized samples Xa' to Xg and VIa, inclusive, shows similar results, indicating that n'=l4 is an economical "upper limit.

EXAMPLE XVIII The seven tetraacrylyl polyamides of Example XIb are submitted to irradiation of the linear accelerator and all of them crosslink in the range of 1 to 3.2'megarads indicating the marked effect of the additional acrylyl groups which not only lowers the dosage requirements but also raises the upper limit of the value of n. The products vary from hard, tough, insoluble, infusible solids at n =1 to tough, infusible, insoluble, progressively more elastic polymers at 11:15.

EXAMPLE XIX A cellulose sponge is impregnated with the telomerized polyamide of Example IXa' dissolved in an equal weight of acetone so that after evaporation of the acetone at 25 C., the sponge contains 18% by weight of the polyamide. On irradiation there is obtained a tough, rigid structural member of low density.

EXAMPLE XX A printed face sheet whose design corresponds to that of a wood grain is impregnated with a mixture of the telomerized polyamide, (l) IXa', 50' parts; (2) IXc, 20 parts; (3) IXd, parts; and (4) IXb where n 2, 5 parts, and alkyd resin G, parts; so that the sheet consists of 60 parts of'polyamide mixture and 40 parts of sheet by weight. This impregnated sheet is laid over a 5 organic solvents.

CH2 OH:

EXAMPLE XXI Parts Alkyd resin A 80 15 Telomerized polyamide, Example III The alkyd resin A and the telomerized polyamide are thoroughly and uniformly mixed and subjected to ioniz- Parts Alkyd resin A 50 Telomerized polyamide (VI) 50 and Alkyd resin A 75 Telomerized polyamide (VI) 25 Compositions of the kind illustrated in this example have the advantage that they do not contain radical initiators and can be stored for long periods of time, and still are readily cured without the addition of catalyst by the simple expedient of subjecting them to irradiation.

EXAMPLE XXII The procedure of Example XXI is repeated except that instead of alkyd resin A, there is used alkyd resin B and infusibility and insolubility is obtained at 3-4 megarads of irradiation.

The compositions of Examples XXI and XXII can be used as room temperature, low pressure laminating resins for the preparation of reinforced laminates from glass mats or fabrics.

It will be understood of course that this invention is not limited to the interpolymerization of alkyd resins A and B with the telomerized polyamide of Example VI, and that another acrylyl telomerized polyamide alone or in combination can be used, for example, thetelomerized polyamides of Examples I, II, and VIIXII, inclusive, can also be used.

In contrast, when the aromatic containing telomerized polyamides of Examples XIII and XIV are used, irradiation doses in excess of 18 megarads are required to produce hard, infusible polymers.

Similarly, high irradiation doses in excess of .16 megarads are required When the aromatic containing alkyd resin J is used with the acrylyl telomerized polyamides in contrast to the use of alkyd resins C, D", E, F, H and I which become infusible and insoluble in the range of 3.8 to 4.0 megarads.

The use of unsaturated alkyd resin G, which is an acrylyl terminated unsaturated alkyd in admixtures with the acrylyl telomerized aliphatic type polyamides, for example, the polyamides of Examples I, II, and VI are particularly beneficial since in all cases crosslinking occurs within the range of 1.8 to 2.1 megarads.

23 EXAMPLE XXIII A smoothly sanded pineboard 12 inches long by 36 inches and %-inch thick is coated on one surface with a mixture of equal parts of the polyamides of Example XI to produce a layer of polyamide 0.005-inch in thickness, and the board is progressed under the sweeping beam of the linear accelerator to be given a uniform dose of '3 megarads. The finished board has the appearance of a high gloss varnished lumber.

24 18 parts of water and 565 parts of caprolactam. The mixture is heated at 200 C. for 0.5 hour. Then 100 parts of succinic anhydride are added and the reaction continued for one hour. The product has the formula To this is added 256 parts of glycidyl acrylate and 1 part of t-butyl catechol and the reaction continued for another two hours to give:

(a) GH CH 0 O CH CIICHzO O C CHgCIIzCOlNII CII2 5C 0150 CHzOHCIIzO O C CH CH When the above polyamide mixture is blended and milled with 60 parts of titanium dioxide pigment (paint grade) and the pigmented polyamide applied to wood, fiber board or concrete block, a porcelainized finish is obtained when the coating is irradiated.

EXAMPLE XXIV Fifty parts of the telomerized polyamide of Example XIa is diluted with parts of glycol dimethacrylate and a concrete panel /s-inch thick is impregnated with this solution and the panel irradiated to a dosage of 3.5 megarads; a water-impervious panel is obtained.

EXAMPLE XXV A mixture of 80 parts of exploded wood fibers of the type used to prepare fiber board, 12 parts of the telomerized polyamids of Example XIIIb, 1 part of zinc stearate and seven parts of linseed oil are milled to uniformity,

By varying the proportion of water, the value of n for the number of repeating units in the center of the molecule can be varied from 1 to 14. Results similar to those described in the respective examples are obtained when the above diacrylyl polyamide is substituted for the diacrylyl polyamides used in Examples VI-VIII, XV and XIX-XXVII.

EXAMPLE XXIX To the reactor of Example XXVIII equipped with a Dean-Stark trap there is added 159 parts of 8-aminocaprylic acid. This is heated at 200 C. until approximately 18 parts of water has been collected in the trap. Then 12.5 parts of succinic anhydride is added and the reaction continued for one hour. Following this 32 parts of glycidyl acrylate and 1 part of t-butyl catechol is added and reaction continued for another two hours to give:

(a) CH CH0 0 O CH2(]lHCH O O C CHZCHZC O[NH(CH2)5C 01 0 CH2CHCH2O O C CII= CH:

pressed into a board and given 4.8 megarads of irradiation. There is obtained a well knit, hard board which is readily paintable with either solvent-type paints, or aqueous emulsion paints.

EXAMPLE XXVI and irradiated to a dose of about 4 megarads. By this process there is obtained a foamed structure in which the By varying the extent to which water is removed in the initial reaction the number of repeating units in the central portion of the molecule can be varied from 1 to 14. Corresponding products are obtained when the above procedure is repeated 2. number of times using in place of the 8-aminocaprylic acid equivalent amounts respectively of S-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid and IO-aminodecanoic acid. Results similar to those described in the respective examples are obtained when these diacrylyl polyamides are substituted for the diacrylyl polyamides used in Examples VI-VIII, XV, and XIX-XXVII.

EXAMPLE XXX The procedure of Example XXIX is repeated using in place of the succinic anhydride 19.4 parts of succinic acid chloride and using 16 parts instead of 32 parts of glycidyl acrylate. The produce has the structure beads are all bonded with infusible bonds to each other, the shape of which conforms to the form of the container.

EXAMPLE XXVII EXAMPLE XXVIII To a reactor equipped with reflux condenser and a means for maintaining a nitrogen atmosphere are added Similar results are obtained as in Example XXIX when the other aminoacids are used and the various tests are performed with these telomerized polyamides. Also by varying the extent to which water is removed from the initial part of the reaction the number of repeating units in the central portion of the molecule can be varied from 2 to 14.

EXAMPLE XXXI Ninety parts of powdered nylon 66 and 10 parts of telomerized polyamide Example IV are thoroughly and uniformly mixed and then melt-extruded into a thin sheet. This sheet is subjected to ionizing radiation. A tough product of improved softening point is produced at 3.5 megarads. Exposure to a dose of 8 megarads produces only a slightly harder product.

25 To improve the heat resistance further the foregoing procedure is modified using a higher ratio of the telomerized polyamide to the nylon 66 as follows:

Parts Nylon 66 80 Telomerized polyamide 20 and Nylon 66 75 Telomerized polyamide 25 EXAMPLE XXXII The procedure of Example XXXI is repeated except that instead of nylon 66, there is used polycaprolactamide, and infusibility and insolubility is obtained at 3-4 mega rads of irradiation.

In contrast, when the aromatic containing telomerized polyamides of Examples XIII and XIV and the acetyl telomerized polyamide of Example Ic are used in Examples XXXI and XXXII irradiation doses in excess of 18 megarads are required to produce hard infusible polymers.

Other methods of combining or mixing the polyamide resins and the diacrylyl polyamides can be used. For example the polyamide resin and the telomerized polyamide can be dissolved in a mutual solvent, such as dimethylformamide and other solvents well known for nylon, and films laid therefrom which can be subsequently radiated.

While certain features of this invention have been described in detail with respect to various embodiments thereof, it will, of course, be apparent that other modifications can be made within the spirit and scope of this inventionand it is not intended to limit the invention to the exact details shown above except as they are defined in the following claims.

The invention claimed is:

1. The highly radiation-sensitive telomerized diacrylyl polyamide having a formula selected from the class consisting of aliphatic hydrocarbon radical having 110 carbon atoms;

R is a divalent saturated aliphatic hydrocarbon radical having 2-10 carbon atoms;

R" is a radical selected from the class consisting of hydrogen and methyl;

X is a radical selected from the class consisting of hydrogen and an acyl radical of the formula R""CO; and

R"" is a radical selected from the class consisting of hydrogen and aliphatic hydrocarbon radical having l-l8 carbon atoms.

2. The telomerized diacrylyl polyamide of claim 1,

which has the formula CHFCHCO O OHzCHCHzO O OOHzOHzCONHCHzCHz NHO C CHzCHzC O O CHzCHOHzO O CCH=CH2 3. The telomerized diacrylyl polyamide of claim 1, which has the formula CHz=OHC O O CHZCHCHZO O O OH2GH2CONHCH2CH2 O O C CH=CH NHO CCHzCHzC O O CHaCHCH O O C CH=CH OCCH=CH 4. The telomerized diacrylyl polyamide of claim 1, which has the formula oH2=cHooooHzofloHgoocomoflgoo [NHCHzOHzNHO C CHzCHzC 01 0 OHzCHCHzO O C CH=CHg 5. The telomerized diacrylyl polyamide of claim 1, which has the formula I I CH C CO 0 CH2$HCHIO O CRCO[ARAO CRO 0].,0 CHzOHCHzO O C 0 =01]:

OX X

OX OX and wherein n has a value of 1-14;

n and n" each has a value of at least 1 and the sum of n and n" is no greater than 14;

A is a divalent radical selected from the class consisting of -O and NH-, there being at least one said NH- radical per polyamide molecule;

R is a divalent saturated aliphatic hydrocarbon radical of 4-10 carbon atoms;

R represents a connecting linkage between two adjacent carboxylic radicals selected from the class consisting which has the formula about 0.5 megarad and no more than about 10 megarads of high energy, ionizing radiation equivalent to at least of a single valence bond and a divalent saturated 100,000 electron volts, of a highly radiation-sensitive telomerized diacrylyl polyamide having a formula selected from the class consisting of 1 out-= o o 0 CHzOHCHzO 0 one O[ARAO UB0 01,.

R o CHzCHCHzO 0 c =CH2 It!) CHZ=(IJ o 0 o ULLMIJHCIIZO 0 ouoomtvoo}.

I 0 c1120 c1120 0 c 0:01p

and

I oHFo o o 0 CHzCHCHzOK) CRNHLJO CRCO[NHRCO]u RI! 0 GHzCHCHzO 0 o (:011:

wherein n has a value of 1-14;

n and n each has a value of at least 1 and the sum of n and n" is no greater than 14;

A is a divalent radical selected from the class consisting of -O- and NH-, there being at least one said NI-I- radical per polyamide molecule;

R is a divalent saturated aliphatic hydrocarbon radical of 4-10 carbon atoms;

R represents a connecting linkage between two adjacent carboxylic radicals selected from the class consisting of a single valence bond and a divalent saturated aliphatic hydrocarbon radical having lcarbon atoms;

R is a divalent saturated aliphatic hydrocarbon radical having 2-10 carbon atoms;

R" is a radical selected from the class consisting of hydrogen and methyl;

X is a radical selected from the class consisting of hydrogen and an acyl radical of the formula R"CO; and

R" is a radical selected from the class consisting of hydrogen and aliphatic hydrocarbon radical having 1 1-18 carbon atoms.

8. The process of claim 7 in which said diacrylyl polyamide is in intimate admixture with a polyamide resin consisting essentially of a plurality of repeating units having a formula selected from the class consisting of --R"CONH and R"NHOCR""CONH wherein R"" is a divalent saturated aliphatic hydrocarbon radical of 4-8 carbon atoms having at least 4 carbon atoms in the linear chain between the two valencies and having a molecular weight of at least 500, said polyamide resin comprising 10-70 percent by weight of the resultant mixture and said diacrylyl polyamide comprising 30-90 percent by weight of the resultant mixture.

9. The process of claim 7 in which said diacrylyl polyamide is intimately admixed with a copolymerizable monomer, said diacrylyl polyamide comprising 1-99 percent by weight of said copolymerizable mass and said copolymerizable monomer comprising 99-1 percent by weight of said copolymerizable mass.

10. The process of claim 7 in which said diacrylyl polyamide is in intimate admixture with an unsaturated aliphatic alkyd resin, said diacrylyl polyamide comprising 10-70 percent by weight of said copolymerizable mass and said unsaturated aliphatic alkyd resin comprising about 30-90 percent by weight of said copolymerizable mass.

28 11. The process of claim 7 in which said diacrylyl polyamide has the formula CHz=CHCOOCHzCHCHzOOCCHzCHzCONHOHzCHz 6H a NHOCCH ClHzCOOCHzfiIHCHzOOCCH UU;

12. The process of claim 7 in which said diacrylyl polyamide has the formula CH2=OHCO O CHzCHCHnOO C CHzCHzCONHCHzCHa OCCH=CH2 NHO C CHzCHzCOO CHzCHCHzO 0 C 011:0]12

O C CH=CH2 13. The process of claim 7 in which said diacrylyl polyamide has the formula [NHCHzCHzNHO C CHzCHzC O]nO CHzCHCHzOO CCH=CHz 14. The process of claim 7 in which said diacrylyl polyamide has the formula O CHzCHCHzO O C CH=CH 15. The process of claim 6 in which said diacrylyl polyamide has the formula CHz=CHCO O CHzCHCHzOlO C (CHmNHkO C CHzCHzCO [NH(CH2)5C OhO CHRCHCHZO C CH=CH2 16. A radiated polymeric product produced according to the process of claim 7.

17. A radiated polymeric product produced according to the process of claim 8.

18. A radiated polymeric product produced according to the process of claim 9.

19. A radiated polymeric product produced according to the process of claim 10.

20. A radiated polymeric product produced according to the process of claim 11.

21. A radiated polymeric product produced according to the process of claim 12.

22. A radiated polymeric product produced according to the process of claim 13.

23. A radiated polymeric product produced according to the process of claim 13.

24. A process for producing an improved polyamide resin composition comprising the treatment with at least about 0.5 megarad ionizing radiation equivalent to at least 100,000 electron volts, of a highly radiation-sensitive telomerized diacrylyl polyamide having a formula selected from the class consisting of and wherein n has a value of 1-14;

n' and n" each has a value of at least 1 and the sum of n and n" is no greater than 14;

A is a divalent radical selected from the class consisting of O and NH--, there being at least one said NH radical per polyamide molecule;

R is a divalent saturated aliphatic hydrocarbon radical of 4-10 carbon atoms;

R represents a connecting linkage between two adjacent carboxylic radicals selected from the class consisting of a single valence bond and a divalent saturated aliphatic hydrocarbon radical having 1-10 carbon atoms;

R' is a divalent saturated aliphatic hydrocarbon radical having 2-10 carbon atoms;

R" is a radical selected from the class consisting of hydrogen and methyl;

X is a radical selected from the class consisting of hydrogen and an acyl radical of the formula R"CO; and

R"" is a radical selected from the class consisting of hydrogen and aliphatic hydrocarbon radical having 1-18 carbon atoms.

References Cited UNITED STATES PATENTS 11/1943 Gray 260-76 8/1941 Lott 260561 US. Cl. X.R.

P0405 H" UNITED STATES PATENT OFFICE 69 CERTIFICATE OF CORRECTION Patent No. 3,471,3 Dated October 7, 1969 Inventorsy). Gaetano F. D'Alelio It is rertified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

olumn 1 line 5 "Pittsburgh, Pa. should be inserted after --PPG INDUSTRIESJI Column 3, line 48 AKHRCQ7 should be ---AiI HRCQ Column 6, line 27 R should be ---R' Column 10, line 47 "Van de Graaff" should be -Van der Graaff--- Column 17, line 22 cmmocco co should be ---CHNHOCCH2CH2--- Column 18, line 14 (a') CH2 =CHC0OCH2CHCH2OOCCH2CO2CONH(CH2) 3 should be (a') CH2 =CHOOCH2CHCH20OCCH2CH2CONI-KCH2) Column 28, line 53 Column 29, line 7 Q7 should be ----OCRCOANHRCQ/ same column 29 line 4 "[OCRNH] should read [oCR NHl SIGNED AND SEALED (SEAL) Attcst:

Edward M. Fletcher, Jr. A Off min-1.1m E. sum. .m.

esung C omissioner of Patents 

